High-temperature reactor



July 14, 1953 K. w. sTooKEY 2,645,566

HIGH-TEMPERATURE REACTOR Filed nec. 12, 194s s sheets-sheet 1 A l* lv f ZJ lNvENToR Kennet/1 moo/fey ATTO NEYS July 14, 1953 K. w. sTooKEY 2,645,566

HIGH-TEMPERATURE REAcToR Filed nec. 12, 1949 s sheets-sheet 2 /5 BY q, @1C

ATTO NEYs July 14, 1953 K. w. sTooKEY HIGH-TEMPERATURE REACTOR v 3 Sheets-Sheet 5 Filed Dec. 12, 1949 Arr NEYs Patented July 4, 195g UNITED STATES PATENT oFFicE 2,645,25 l' y HIGH-TEMnA'rURiritsrlcfron` Kenneth W. smokey, cleveland; ohio, assigner te* The Gas Machinery Company, Cleveland, Ohio, a corporation of Ohio Applieation December 12, 1949 ,flse'iai'1ve- 132.5153l` rcleims. (ci. 23-277) The present invention relates to a new and novel reactor for continuously carrying out thermal reactions and to the method of carrying out such reactions therein. More particularly this invention relates to a continuous reactor and to the method for carrying out high temperature reactions therein at '2000 F. up to about 3000 F. and at even higher temperatures.

In the past continuous tubular reactors for carrying out high temperature reactions have been constructed with metal alloy tubes which are capable of withstanding temperatures upto about l800 F. Temperatures in excess of 2000 have not been practical in such reactors since the tubes failed due to loss of strength and chem.- ical action at the elevated temperatures. Thus tubular reactors for continuous-commercial processes have been used only when temperatures below 2000 F. have been employed. e

In an effort to overcome the failure of the metal alloy tubes used in the prior art reactors it has been suggested that the tubes be suspended from the top instead of being supported at the bottom so as to reduce the load thereon, thusV enabling the use of slightly higher temperatures before complete failure of the metal tubes. Temperatures in excess of 2000 F. are not possible even with this improvement.

In the reactor of the present invention it is possible to carry out continuous thermal reactions of uid reactants at higher temperatures 4'than was possible heretofore. tubes which may be of any suitable material which will withstand the high temperatures, such as a refractory material. It has been found, however, that silicon carbide tubes, sometimes known by the trade name Carborundum, are well suited for the present invention since they possess suitable heat transfer characteristics and also have the necessary strength at high temperatures and are chemically inert.

Another feature of the present invention is that e the reactor may be divided into two or vmore transverse sections, each of which may be heatedA to different temperatures whereby the temperature within the reaction vtube will varyfrom Grenerally` the reactants are passed through one or more 1 The reactor contains top to bottom as may be desired for any particular' operation.

According to the present invention temperatures well in excess Vof 2000 F. and as high as 3000" F. and higher are possible in a reactor, the tubes of which are supported partially or entirely at the bottom thereof. Y

In areactor according to the present inventionitis possible to carry out many reactions not previously possible on acommercial scale and also to carry out known commercial processes in a far more eiiicient and economical mannery For example the reactor may be used for high temperature cracking of hydrocarbons to hydrogen and carbon in almost theoretically quantitative yields. Not only is the yield of hydrogen and carbon very high but the-cracking step, due to the high temperatures used, i. e. from about 2200 F. to about 2700o F., can be carried out in much shorter time than heretofore, whereby the total output of the reactor is far greater than prior reactors of similar size. V

It will be understood that various reactions can be carried out in the absence of avcatalyst in which case the tube passage may be completely open or may be partially or entirely lled with pieces of inert refractory material known as core- 1 reactionsrequire a catalyst and in this` case, the l' desired catalyst may beplaced within the tube for contact -by the fluid reon suitable carriers actants.

Itis, therefore, an object of the presentv invention to provide a reactor in which reactionsy may be carried out at temperatures above 2000 F1 up to 3000 F. and higher. f

ture reactions.

Still'another object of the invention is to pro-V vide a reactor and method-for employing same in which the heating zone is divided `into sections the temperaturesof each of which may be controlled within certain limits.

Still another'object is to provide a high tem- Another object of the invention is the use of tubes composed of aligned sections having gas tight joints between the abutting ends thereof.

Other objects of the invention will be apparent from the following detailed description and the accompanying drawings in which,

Figure 1 is a side elevation, partly in cross section of a reactor according to the present invention,

Figure 2 is an enlarged horizontal cross sectional view taken along line 2--2 of Figure l,

Figure 3 is an enlarged vertical cross sectional view of the lower part of the reactor shown in Figure 1, taken along line 3 3 of Figure 2,

Figure 4 is an enlarged top plan view partly broken away of the reactor shown in Figure .1,

Figure 5 is an enlarged verticalcross sectional View of the upper part of the reactor shown in Figure 1 taken along line 5 5 of Figure 4,

Figure 6 is a side elevation, partlyin section of a modified reactor tube for use in the reactor shown in Figure 1,

Figure 7 is a plan view of the reactor tube shown in Figure 6, and

Figure 8 is a vertical section of a modification of a portion of the reactor shown in Figure 5.

Referring to Figure 1, the reactor II which rests upon supports I2 comprises a refractory lined shell I3. At spaced intervals throughout the length of the shell I3 there are provided horizontal walls I4 preferably of refractory materials which divide the inside of the shell I3 into lsections as will be described more fully hereinafter. The particular number of walls I4 employed will depend upon the nature of the desired reaction to be carried out and may vary from four, as shown in Figure 1, or even more, down to one, or in the case of small reactors or relatively short reactors the dividing walls may be eliminated altogether. Reaction tubes I5 extend throughout the shell I3 and pass through the top I6, the bottom I1 as well as through suitable openings I8 in the Walls I4.

The number of reaction tubes may vary in accordance with the desired capacity of the reactor. Although three reaction tubes I5 have been shown it will, of course, be understood that a greater or lesser number may `be used under certain conditions or, if desired .only one reaction tube may be used.

In the wall of the shell I3 are arranged one or more burners I9 or the like for the combustion of a fuel, such as a petroleum oil or other uid fuel, for supplying heat tothe reactor. If desired, one or more burners may be disposed in each section of the reactor; two burners having been shown in Figure 1 merely for illlustrative purposes. It is also contemplated that some of the sections may not have any burners or that the burners in any one section may not be used at all times.

The dividing walls I4 are provided with openings for the passage of combustion gases from one section to the next in a downward direction while providing a bafiling effect. As shown in the drawings a flue 2| is provided at thebottom of the reactor II for withdrawing the combustion gases. It will be seen therefore that the combustion gases, no matter in which section the burner or burners I9 may be located, will move in a generally downward direction, modied by turbulence and bafliing, through the reactor II to the flue 2 I.

The burners I9 are preferably placed in the Wall of the shell I3 so that the flame and combustion gases will be directed tangentially rather than radially. Such an arrangement eliminates localized .hotspots in the reaction tubes which prevents possible backflow of gas.

sired temperature.

might cause possible failure of the tubes and it also provides a more uniform heating of the tubes in any one section.

By varying the number of burners I9 in the various sections or by varying the temperature of combustion by varying the air-fuel ratio, it is pos-sible to vary the effective temperature of the tube at different points. Under some circumstances it may be desirable to increase the temperature of the reaction tube from top to bottom, while under different circumstances the reverse maybe desirable. Still again it may be desirable to provide the hottest section at or near the midpoint of the reaction tube.

The reaction tubes I5 may be of any desired material which will withstand the maximum de- However, one of the most suitable materials available today are refractory materials, such as silicon carbide, sometimes known to the trade as carborundum This material Ymay be shaped into tubes or tube sections which can be employed in the present reactor.

Frequently it will be desirable to employ a reactor of substantial height, such as 25 or 30 feet or higher. In thisA case it may be desirable to utilize reaction tubes composed of two or more aligned sections, superimposed on each other y and abutting end to end.'y In order t0 obtain a gas proof joint between the sections of refractory tubing it has been found that a ball and socket joint may be used as shown and described, for example, in United States Patent No. 2,472,497 granted to K. W. Stookey. This joint essentially comprises one convex tube end and one concave .tube end which fit to form a gas proof joint while still permitting a limited amount of angular movement between adjacent sections. The use of continuous refractory tubes of lengths in excess of eight or ten feet is4 generally not satisfactory with available materials. Not only is the construction and formationr of such tubes impractical but also they are more likely to be affected adversely by the operating conditions in the reactor.

When reaction tubes in sections are used it is generally preferable though not essential that the tube section joints be located in the dividing wall I4 as shown in Figures l and 3.

Referring more particularly to Figure 3, the details of the bottom of the reactor II are more clearly shown. The reaction tubes I5 extend down into the refractory lining at the bottom of the shell and rest upon dip pipes 22 which are secured, by welding or the like, to the bottom plate II. The pipes 22 extend downwardly from the bottom of the reactor into the water seal 23 to a point beneath the water level maintained therein. The water seal 23 affords a degree of control on the pressure in the reaction tubes,`

quenches the gaseous products and cleans the gas by collecting condensibles and solid matter which might be contained in the gaseous products and The product gas is removed from the system through linev 24.

Referring particularly to Figures 4 and 5, the reaction tubes I5 project through the top of the shell I6 and are provided with seals '25, such as sand seals, for accommodating thermal linear tained in an annular trough 29 mounted on the top of the'shell IE. Above the plate 26, a header 3B is provided into which one or more of the fluid reactants can be introduced. In the modication illustrated a hydrocarbon oil may be introduced thru lines 3l, steam may be introduced through lines 32 and air, C02 or other gas may be introduced through lines 33. Each of the lines 3l, 32 and 33 are provided withv ilexible sections to compensate for linear expansion of the reaction tube. As seen inFigure 5, the oil line 3| may extend downwardly intov the reaction tube I5 while the gaseous reactants can be introduced tangentially into the header 30. It will be understood that the gaseous reactants may be pre-mixed and/or preheated whenever desired.

Although the invention has been described and illustrated with reference to a reaction involving oil, steam and air, CO2 or other gas it will be understood that these reactants are merely given by way of illustration and that other reactants or a single gas or fluid can be treated, such as, for example, the thermal treatment of propane or other hydrocarbon fluid.

With particular reference to Figures 3 and 5 it will be seen that the refractory lining of shell 3l and the refractory walls I4 are provided with tapered openings I8 and Ia through which the reaction tubes I5 pass, lthe smallest portion of the opening being slightly larger than the tube to allow for lateral thermal expansion thereof. The tapered porti-ons of the openings IB and I8a permit a more gradual change in temperature between those portions of the tubes I 5 which are more directly exposed to the hot combustion gases and those portions of the tubes which are not in such direct contact with said gases.` Y

The dividing walls I4 are preferably made `of refractory material and, as shown in the drawhot combustion gases entery the section or sections, between the walls I4, tangentially and swirl around the tubes I5 ina generally down-` wardly spiral manner and are funnelled through gas openings V20 to the next` lower section and finally to the ilue 2|. It will be clear that the temperature of any section may .be controlled by ings, are provided with a centralopening 20 for passage of the hot lcombustion gases and with spaced openings I8 around the central opening for the reaction tubes I5. Of course, more or less than three reaction tubes may be used when desired. However, when one tube is employed water in the seal 23.

it will generally pass through the centers of the i shell I3 and walls I4 and gas passage openings in the walls I4 will be provided around the central v tube I5.

With reference to the Figures 6 and 7, the tube I5 may be provided at or near the bottom thereof with a grid 34 which is generally composed of the same refractory material as the tube. When catalytic reactions are to be carried out, the catalyst, supported on carrier particles, is placed in the tubes on the grid. One suitable carrier for the catalyst is aluminum oxide which may have the shape of conventional Raschig rings.

Occasionally it may be desirable t-o bleed off some of the initial gases or vapors formed when the hydrocarbon oil is rst vaporized in the reactor and before the oil vapors or gases have been fully treated in the reactor. Such initial gases may be used for any desired purpose and may for example be blended with the nal product gases. To accomplish this a bleed tube 35 as shown in Figure 8 may be employed. The apparatus shown in Figure 8 corresponds with that shown in Figure 5 except for the tube 35, which extends down int-o refractory tube I5 about the same distance as and parallel to line 3I. The initial gases are drawn into tube 35 and are withdrawn as indicated by the arrow.

In operation one or more of the burners I9 are controlling .theburners I9 .in the respective sections. As thetemperature rises the tubes expan-d both laterally and longitudinally. Since the tubes I5 are supported .by the dip pipes 22 at the bottomof the reactor the longitudinal expansion takes place in an upward direction. The sand seal 25 permits this expansion while keeping the inside of the reactor sealed The header 30 and inlet lines 3|, 32 and 33, by virtue of the iiexible sections are permitted to rise with the expansion. The lateral expansion is accommodated by the openings I8 and Ia. Should there be any tendency for the tubes I5 to become distorted or bent by compression caused by the springs 2B, this is overcome by the ball and socket joints between the tube sections which permits limited angular movement between the sections.

When the sections of the reactor I I and tubes I5 have reached the desired temperatures, the reactants are introduced into the top of the reaction tubes I5 as described hereinbefore and pass y downwardly through the tubes while being treated thermally and/or catalytically. The product gases are quenched and washed when they pass through the water seal 23 and finally to outlet pipe 24. Any water vapor which may accompany the product gases may be removed by conventional condensers or the like. o This method will, of course, produce relatively cool product gases. If it is desired that the product gases have a relatively high temperature, this can be accomplished by using a higher boiling liquid than For example, tetra-cresyl silicate, inhibited orthodichlor benzene,silicone liquids, a eutectic mixture of 73.5% phenyl ether and 26.5% of diphenyl or the like may be used in place of water. Also, if desired the product gases may be passed directly from the dip pipe 22 to an indirect heat exchanger, thus eliminating the seal 23 altogether and providing a controlled cooling of the product gases.

A commercial unit based on the present invention would, of course, include manholes, peepholes. temperature indicators, means for periodically cleaning the reaction tubes and other conventional appurtenances, which have not been shown for purposes of simplification.

Although the reactor and the method of carrying out thermal reactions therein have been described with particular reference to the modication shown in the attached drawings, it will be understood that this modification is merely illustrative and that the scope of the present invention is dened in the appended claims.

What is claimed is:

1. Apparatus for continuously treating fluids at high temperatures comprising an elongated refractory lined shell, at least one tube disposed longitudinally therein and extending through the ends of said shell, inlet means for introducing fluids to be treated into one end of said at least one tube, exit means for withdrawing the treated fluidsV from the other end of said at least one tube, at least one refractory dividing wall extending transversely of said shell so as to divide said shell into a plurality of sections, at least one burner. disposedin each of said sections for sup-:..-

plying heat to said at least one tube, saidcl' said dividing walls having openings therein for least one dividing wall having atleast one opening for passage therethrough of' each of saidtubes, and having aV port to afford free communication between adjacent sections and exitnreans for withdrawing the combustion gases derived from the operation of said burners from said shell at a point adjacent the exit meansfor withdrawing said treated fluids from said tube whereby the combustion gases may pass from one section to the adjacent section in a direction concurrent with the flow of fluids in said tube.

2. Apparatus for continuously treating fluids at high temperatures comprising an elongated refractory lined shell, at least one tube disposed longitudinally thereinfand extending through the ends of said shell, inlet means for introducing fluids to be treated into one end of said at least one tube, exit means withdrawing the treated uids from the other end of said at least one tube, at least two refractory dividing walls extending transversely of said shell so as to divide said shell into at least three sections, at least one burner disposed in each of said sections. for supplying heat to said at least one tube, said dividing walls having at least one opening for passage therethrough of each of said tubes, and having a port to afford free communication between adjacent sections and exit means for withi drawing the gases derived from the operation of said burners from said shell at a point adjacent the exit means for withdrawing said treated uid's from said tube whereby the combustion gases pass fromone section to the adjacent sec- 35 at least oneburner disposed in each of said sections for supplying heat to said tubes, each of passagetherethrough of each of said tubes and having a central port'to afford free communication between adjacent sections and exit means for withdrawingY the combustion gases derived from the operation of said burners from said Shell at a point adjacent the exit means for withdrawingsaid treated iiuids from said tube where- 7. Apparatus as claimed in claim 5 wherein each of said refractory tubes is composed of a plurality of superimposed sections abutting end to end, the junctions of said sections being disposed within the openings in said dividing walls.

KENNETH W. STOOKEY.

References cited in the me of this patent UNITED STATES PATENTS Number Name Date 583,915 Loomis June 8, 1897 986,489 Morehead Mar. 14, 1911 1,307,362 Kaufman June 24, 1919 1,495,776 Burdick May 27, 1924 1,496,609 Sharp et al June 3, 1924 1,843,083 Burke et al Jan. 26, 1932 v2,028,326 lHanks Jan. 21, 1936 2,173,984 .Shapleigh Sept. 26, 1939 2,293,421V v Baetz Aug. 18, 1942 FOREIGN PATENTS yNumber e Country Date 301,969 Y Great Britain Dec. 13, 1928 7,983 Great Britain Mar. 1892 505,377 France July 1920 505,378 France July 1920 

1. APPARATUS FOR CONTINUOUSLY TREATING FLUIDS AT HIGH TEMPERATURES COMPRISING AN ELOGATED REFRACTORY LINED SHELL, AT LEAST ONE TUBE DISPOSED LONGITUDINALLY THEREIN AND EXTENDING THROUGH THE ENDS OF SAID SHELL, INLET MEANS FOR INTRODUCING FLUIDS TO BE TREATED INTO ONE END OF SAID AT LEAST ONE TUBE, EXIT MEANS FOR WITHDRAWING THE TREATED FLUIDS FROM THE OTHER END OF SAID AT LEAST ONE TUBE, AT LEAST ONE REFRACTORY DIVIDING WALL EXTENDING TRANSVERSELY OF SAID SHELL SO AS TO DIVIDE SAID SHELL INTO PLUARLITY OF SECTIONS, AT LEAST ONE BURNER DISPOSED IN EACH OF SAID SECTIONS FOR SUPPLYING ONE DIVIDING WALL HAVING AT LEAST ONE OPENLEAST ONE DIVIDING WALL HAVING AT LEASTA ONE OPENING FOR PASSAGE THERETHROUGH OF EACH OF SAID 